N-hydroxyethyl derivative of aminohydroxybenzenes



may 14, 1929. uNrrs STATES 1,712,716 PATENT OFFICE.

GUSTAV REDDETJIEN AND WERNER MUELLER, OF LJElIPZIG, GERMANY, ASSIGNORS, BY MESNE ASSIGNMENTS, T0 AGFA ANSCO CORPORATION, OF BINGHAMTON, NEW

YORK, A CORPORATION OF NEW" YORK.

N-HYDBOXYETHYL DERIVATIVE OF AMINOHYDROXYBENZENES.

m Drawing. Application filed November 2, 1927, Serial No. 230,635, and in Germany November 19, 1926.

This invention relates to new N-hydroxyethylderivatives of aminohydroxybenzenes corresponding to the general formula x HO. oH1-no2- 011 wherein X represents hydrogen or the group -CH -CH -OH, and to the manufacture of these products.

The new bases are made by condens ng a highly active derivative of ethane containing one atom of oxygen and containing 111 then molecule the atom figuration IMO-CH2 comprising halogen hydrin 0t glycol and ethylene oxide at ordinary or raised temperature with an aminohydroxybenzene; in some cases it is advantageous that an agent that binds acid should be present and there may also be used a diluent, a solvent or a catalyzer.

The following examples illustrate the manufacture of the new compounds the parts being by weight Ewample 1.110 parts of i-amino-l-hydroxybenzene are mixed with 250 parts of ethylene chlorhydrin and 53 parts of anhydrous sodium carbonate and the mixture 1s heated in a reflux apparatus until it boils feebly. The reaction occurs quickly and after a few hours the product can be precipitated in thick brownish crystals by mixing the mass with cold saturated sodium carbonate solution. By recrystallization from boiling water and decolorizing by means of charcoal the colourless crystals of the 4:- [di- (hydroxyethyl) ]-amino-1-hydroxybenzone are obtained of melting point 140 C. The new base is soluble in water, acids and alkalies to a completely colourless solution. It is remarkably stable in dry condition and its solution also remains unchanged in air.

Example 2.-110 parts of, .t-ammo-Lhydroxybenzene are mixed with a solution of parts of potassium hydroxide in 500 parts of alcohol and 81 parts of ethylene chlorhydrin in 100 parts of alcohol are added. Very soon potassium chloride begins to separate and the reaction can be quickly completed by heating; After separating the po tassium chloride from the cold solution the product of the reaction may be precipitated in the form of sulphate from the solution by addition of 4649 parts of concentrated sulphuric acid. By dissolving the sulphate in a little hot water and neutralizing with a solution of sodium carbonate of 10 per cent strength and cooling, a small quantity of unchanged l-amino-1-hydroxybeuzene can be recovered. Of the filtration the new base may be extracted from the filtrate by a suitable solvent from which it is obtained in the form of brownish crystals; when recrystallized from a mixture of cthylacetate and chloroform it forms colourless crystals of n'ielting point 904)? C. It is 4-(hydroxyethyl)-amino-l-hydroxybenzenc. It is extraordinarily soluble in water, acids, alkalies,

alcohol, ethylacotate and other solvents, but insoluble in benzene and benzinc. Its sulphate contains half a molecular proportion of sulphuric acid and is soluble in much alcohol from which solution it may be obtained in the form of long slender prisms.

Ea'ample 3.-109 parts of l-amino-l-hydroxybcnzene suspended in 1000 parts of water are mixed with 5 parts of calcium carbonate. Whilst stirring slowly a stream of ethylene oxide. is introduced until the l amino-l-hydroxybenzcne is completely converted into the l-[di-(l1ydroxyethyl)]-a1nino-1-hydroxybenzene.

The ethylene oxide in excess is removed by heating to the boiling point. The product of reaction dissolves and is filtered oil from the residue. After cooling the 4-[di- (hydr0xyethyl) -amino-l-hydroxybenzene is separated in thick nearly colourless crystals. From the filtrate the remaining part of the product of reaction may be obtained by evaporation or by extraction with ethylacetate. By recryside is introduced at a temperature of C. 1m

The 4 [di (hydroxyethyl)] amino -1- hydroxybenzene thus obtained is purified in the manner described in Example 8.

Example 5.-109 parts of 4-amino-1-hy droxybenzene, 1000 parts of water, 5 parts of concentrated sulphuric acid and 1 part of mercuric acetate are mixed and heated to 60' 70 C. Whilst stirring a strong stream of ethylene oxide is introduced. After a short time the 4- (hydroxyethyl) amino-l-hydroxybenzenehas been formed. The introduction of ethylene oxide is stopped if 4-[di-(hydroxyethyl)]-amin0-l-hydroxybenzene begins to be formed. After heating to the boiling point the solution is neutralized with sodium carbonate, filtered and cooled. After three hours the unchanged 4-amino-l-hydroxybenzene and some 4- [di- (hydroxyethyl) ]-amino-l-hydroxybenzene are separated by filtration, the filtrate is evaporated in vacuo to dryness and the organic residue is dissolved in 400 parts of alcohol. To the alcoholic solution slowly 2025 parts of concentrated sulphuric acid are added at a temperature of 15'25 C. The 4- (hydroxyethyl)amino-1- hydroxybenzene separates as sulphate in the form of thick brownish crystals. It maybe reta-ystallized from alcohol of 8090 per cent strength and is identical with the product described in Example 2.

Erample 6.In a suspension of 109 parts of et-amino-l-hydroxybenzene in 1500 parts of water a stream of ethylene oxide is introduced at a temperature of C. until the 4- amino-1-11ydroxybenzene is no more to be found in the reaction. vessel. 'The aqueous solution of the product of reaction. a mixture of 4-[di-(l1ydroxyethyl)]-amino-1-hydroxybenzene and 4-(hydroxyeth vl)-auiino-l-hydroxybenzene, is heated to the boiling point, filtered and cooled. The greater part of 4- I di-thydroxyethyl) ]-amino l hydroxybenzene is separated in the form of thick nearly colourless crystals which are separated from the aqueous solution containing the 4-(hydroxyethyl)aniino-l-hydroxybenzene. It is finished in the usual manner.

Example '7.109 parts of Q-amino-l-hydroxybenzene are heated with 130 parts of calcium carbonate. 2000 parts of water and 102 parts of ethylene chlorhydrin slowly to the boiling point and boiled in a reflux apparatus until the ethylene chlorhydrin has disappeared. After 2 to 3 hours 110 parts of sodium carbonate are added to the hot mixture. Calcium carbonate is separated and filtered olt'from the hot solution. After cooling the 2-[di-(hydroxyethyl)]-amino-1- hydroxybenzene is extracted from the solution by means of ethylacetate. It is in the unpurified state a brownish oil; its purified sodium salt, made by addition of sodium hydroxide forms colourless laminated crystals which are decomposed at a ten'lperature above 240 C. They are easily soluble in water, alkalies and acids.

Laumple 8.109 parts of 2-amino-1-hydroxybenzene are mixed with 60 parts of calcium carbonate and 1000 parts of boiling water. 81 parts of ethylene chlorhydrin being added. After boiling for some hours. 55 parts of sodium carbonate and then 500 parts of boiling water are added. The separated .calcium carbonate is filtered off. From the yellowish brown filtrate after coolin the 2- (hydroxyethyl) amino 1 ha'droxy nzene and some Q-[di-(hydroxyet yl)]-amino-1- hydroxybenzene are extracted with ethylacetate. The recrystallized 2- ('hydroxyethyl) amino-l-hydroxybenzene forms laminated crystals of melting point 81 C. The base is easily soluble in water, acids and alkalies, alcohol, ethylacetate, acetone and difiicultly soluble in chloroform, benzene. Its sulphate recrystallized from dilute alcohol forms small slender prisms, easily soluble in water.

Example 9.In a suspension of 109 parts of 2-amil1o-1-hydr0xybenzene in 1500 arts otwater after addition from 5 parts oFcalcium carbonate a stream of ethylene oxide is introduced whilst stirring at a temperature of (Kl-70 C. until the 2-amino-1-hydroxybenzene is completely converted into the. 2- [di- (hydroxyethyl)] amino -1 -hydroxybenzenc. After boiling and filtration parts of a solution of sodium hydroxide of 36 Be. strength is added. The sodium compound of the product. of reaction is separated in form of nearly colourless laminated crystals. A saturated solution of sodium chloride is added and a ttcr cooling the crystals are separated by filtration. The recrystallized product is identical with that described in Example 7.

121mm pic 10. 160 parts of Q-amino-lliydroxybenzene-sulphate are heated with 1000 parts of water to 7 0 C. Vhilst stirring a. stream of ethylene oxide is introduced which is stopped it 2 [di-(hydroxyethyl)]-aminol -hydroxybenzene begins to be formed. The solution is heated to the boiling point. neutralized with sodium carbonate and filtered. After cooling the clear solution is extracted with ethylacetate. The Q-(hydroxycthyl)aniino-l-hydrohenzene obtained from the extract in the usual manner is identical with that described in Example 8.

A loss of ethylene oxide applied in Examples 3, 4, 5, 6, 9 and 10. is avoided by employing a battery of reacting vessels following one the other.

What we claim is 1. The new N -hydroxyethylderivatives of aminohydroxyben'zenes corresponding to the general formula x HOCIH|'N\ om-cm-on wherein X represents hydrogen or the group -CH -CH -OH being colourless products soluble in water, acids and alkalies to colourless solutions, being stable when exposed to air, their solutions also remaining unchanged in air.

2. The new N-hydroxyethylderivatives of aminohydroxybenzenes corresponding to the general formula OHrCIh- OH forming in the dry state colourless crystals,

easily soluble in water, acids, alkalics, alcohol, acetone, ethylaoetate, forming with sulphuric acid a colourless salt which recrystallized from alcohol forms colourless prisms easily soluble in water.-

3. The new N-hydroxyethylderivatives of 4-amino-1-hydroxybenzene corresponding to the general formula wherein X represents hydrogen or the group -CH -CH OH being colourless crystallized products soluble in water,'acids and alkalies to colourless solutions, being stable in dry condition, their solutions also remaining unchanged in air.

4:. The new N-hydroxyethylderivative of a-amino-l-hydroxybenzene corresponding to the formula n N CH2- omon forming colourless crystals of melting point 9697 C., easily soluble in water, acids, alkalies, alcohol, ethylacetate, difficulty soluble in benzene, benzine, forming with sulphuric acid a salt which contains half a molecular proportion of sulphuric acid and which is soluble in much alcohol from which solution it may be obtained in the form of long slender prisms.

5. A manufacture of N-hydroxycthylderivatives of aminohydroxybenzenes by con- (lensing aminohydroxybenzenes with a highly active derivative of ethane containing one atom of oxygen and containing in their molecule the atom figuration comprising halogen hydrin'of glycol and ethylene oxide.

6. A manufacture of N-hydroxyethylderivatives of aminohydroxybenzenes by condensing aminohydroxybenzenes with a highly active derivative of ethane containing one atom of oxygen and containing in their molecule the atom figuration Hill-CH2 comprising halogen hydrin of glycol and natures.

comprising halogen hydrin of glycol and ethylene oxide. a

10. A manufacture of N-hydroxyethylderivatives of el-amino-l-hydroxybenzene by condensing 4-amino-1-hydroxybenzene with a highly active derivative of ethane containing one atom of oxygen and containing in their molecule the atom figuration Hail-CH2 comprising halogen hydrin of glycol and ethylene oxide in the presence of an agent that binds acid.

11. A manufacture of N-hydroxyethylderivatives of el-amino-l-hydroxybenzene by condensing 4-amino-1-hydroxybenzene with chlorhydrin of glycol.

'12. A manufacture of N-hydroxyethylderivatives of 4-omino-1-hyd.roxybenzene by condensing lamino-Lhydroxybenzene with chlorhydrin of glycol in the presence of an agent that binds acid.

13. The manufacture of 4- (hydroxyethyl) amino-l-hydroxybenzene by condensing molecular proportions of 4-amino-1-hydroxybenzene and chlorhydrin of. glycol.

In testimony whereof, we affix our sig- GUSTAV REDDELIEN. WERNER MUELLER.

U 1 7 t Certificate of Patent'No."1,71-2,716. e I

GUSTAV REDDELIEN ET AL. I It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

."Page-l, line 5,'f orthe formula I I X Y read HO-O -N eron 0H,-0H,-0H;

4 v I 1 w r page 3, line 91, cleim' 12; for 4 omino-1-hydroxybenzene read 4-ami1w 1 kydrozgbenzene; and that theflsaid Letters Patent should be read with these corrections therein that theilsame may conform to the record of the casein the Patent Oflice.

Signed and ,siehledthis 25th da'y of June; A. 1929. I Y i M. J. MOQRE, v [SHALL t Acting floiurtiaaioner of Patents.

Granted'May 14, 1929, m 

